The invention relates to novel substituted benzoyl ketones, to processes for their preparation and to their use as herbicides.
It is already known that certain substituted benzoyl ketones have herbicidal properties. (cf. EP-A-625505, EP-A-625508, U.S. Pat. No. 5,804,532, U.S. Pat. No. 5,846,906, WO-A-96/26193). However, the activity of these compounds is not entirely satisfactory.
This invention, accordingly, provides the novel substituted benzoyl ketones of the formula (I), 
in which
n represents 0, 1, 2 or 3,
A represents a single bond or represents alkanediyl (alkylene),
R1 represents hydrogen or represents in each case optionally substituted alkyl or cycloalkyl,
R2 represents hydrogen, cyano, carbamoyl, halogen, or represents in each case optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl,
R3 represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino or dialkylaminosulphonyl,
R4 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino or dialkylaminosulphonyl, and
Z represents an optionally substituted 4- to 12-membered, saturated or unsaturated, monocyclic or bicyclic, heterocyclic grouping which contains 1 to 4 hetero atoms (up to 4 nitrogen atoms and optionallyxe2x80x94alternatively or additionallyxe2x80x94one oxygen atom or one sulphur atom, or one SO grouping or one SO2 grouping) and which additionally contains one to three oxo groups (Cxe2x95x90O) and/or thioxo groups (Cxe2x95x90S) as components of the heterocycle,
including all possible tautomeric forms of the compounds of the general formula (I) and the possible salts of the compounds of the general formula (I).
In the definitions, the hydrocarbon chains, such as alkyl or alkanediyl, are in each case straight-chain or branchedxe2x80x94including in combination with heteroatoms, such as in alkoxy.
n preferably represents 0, 1 or 2.
A preferably represents a single bond or represents alkanediyl (alkylene) having 1 to 4 carbon atoms.
R1 preferably represents hydrogen, represents optionally cyano, carboxyl, carbamoyl, halogen, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkylsulphonyl-substituted alkyl having 1 to 6 carbon atoms, or represents optionally cyano-, carboxyl-, carbamoyl-, halogen-, C1-C4-alkyl- or C1-C4-alkoxy-carbonyl-substituted cycloalkyl having 3 to 6 carbon atoms.
R2 preferably represents hydrogen, cyano, carbamoyl, halogen, represents in each case optionally cyano-, carbamoyl-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy or alkoxycarbonyl having in each case up to 6 carbon atoms, or represents in each case optionally halogen-substituted alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms.
R3 preferably represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, represents in each case optionally halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkylsulphonyl-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case up to 4 carbon atoms in the alkyl groups, or represents alkylamino, dialkylamino or dialkylaminosulphonyl having in each case up to 4 carbon atoms in the alkyl groups.
R4 preferably represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, represents in each case optionally halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkylsulphonyl-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case up to 4 carbon atoms in the alkyl groups, or represents alkylamino, dialkylamino or dialkylaminosulphonyl having in each case up to 4 carbon atoms in the alkyl groups.
Z preferably represents one of the heterocyclic groupings below 
where the dotted line is in each case a single bond or a double bond, and each heterocyclic grouping preferably only carries two substituents of the definition R5 and/or R6,
Q represents oxygen or sulphur,
R5 represents hydrogen, hydroxyl, mercapto, cyano, halogen, represents in each case optionally cyano-, halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkylsulphonyl-substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case up to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkylamino or dialkylamino having in each case up to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl, alkinyl, alkenyloxy, alkenylthio or alkenylamino having in each case up to 6 carbon atoms in the alkenyl- or alkinyl groups, represents in each case optionally halogen-substituted cycloalkyl, cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylthio or cycloalkylalkylamino having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally up to 4 carbon atoms in the alkyl moiety, or represents in each case optionally halogen-, C1-C4-alkyl- or C1-C4-alkoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, orxe2x80x94if two adjacent radicals R5 and R5 are located at a double bondxe2x80x94together with the adjacent radical R5 also represents a benzo grouping, and
R6 represents hydrogen, hydroxyl, amino, alkylideneamino having up to 4 carbon atoms, represents in each case optionally halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylamino, dialkylamino or alkanoylamino having in each case up to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl, alkinyl or alkenyloxy having in each case up to 6 carbon atoms in the alkenyl- or alkinyl groups, represents in each case optionally halogen-substituted cycloalkyl, cycloalkylalkyl or cycloalkylamino having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally up to 3 carbon atoms in the alkyl moiety, or represents in each case optionally halogen-, C1-C4-alkyl- or C1-C4-alkoxy-substituted phenyl or benzyl, or together with an adjacent radical R5 or R6 represents optionally halogen- or C1-C4-alkyl-substituted alkanediyl having 3 to 5 carbon atoms,
where the individual radicals R5 and R6xe2x80x94if a plurality of them are attached to the same heterocyclic groupingxe2x80x94can have identical or different meanings within the scope of the above definition.
Q preferably represents oxygen.
R5 preferably represents hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine, bromine, iodine, represents in each case optionally fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, methylthio-, ethylthio-, n- or i-propylthio-, n-, i-, s- or t-butylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, represents methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, di-n-propylamino or di-i-propylamino, represents in each case optionally fluorine- and/or chlorine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl, butinyl, propenyloxy, butenyloxy, propenylthio, butenylthio, propenylamino or butenylamino, represents in each case optionally fluorine- and/or chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or represents in each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, methoxy-, ethoxy-, n- or i-propoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, orxe2x80x94if two adjacent radicals R5 and R5 are located at a double bondxe2x80x94together with the adjacent radical R5 also represents a benzo grouping.
R6 preferably represents hydrogen, hydroxyl, amino, represents in each case optionally fluorine- and/or chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino or dimethylamino, represents in each case optionally fluorine- and/or chlorine-substituted ethenyl, propenyl, ethinyl, propinyl or propenyloxy, represents in each case optionally fluorine- and/or chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, methoxy-, ethoxy-, n- or i-propoxy-substituted phenyl or benzyl, or together with an adjacent radical R5 or R6 represents in each case optionally methyl- and/or ethyl-substituted propane-1,3-diyl (trimethylene), butane-1,4-diyl (tetramethylene) or pentane-1,5-diyl (pentamethylene).
n particularly preferably represents 0 or 1.
A particularly preferably represents a single bond, methylene, ethylidene (ethane-1,1-diyl) or dimethylene (ethane-1,2-diyl).
R1 particularly preferably represents hydrogen, represents in each case optionally cyano-, carboxyl-, carbamoyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally cyano-, carboxyl-, carbamoyl-, fluorine-, chlorine-, methyl-, ethyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
R2 particularly preferably represents hydrogen, cyano, carbamoyl, fluorine, chlorine, bromine, represents in each case optionally cyano-, carbamoyl-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or represents in each case optionally fluorine- and/or chlorine-substituted methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl.
R3 particularly preferably represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, represents in each case optionally fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy, represents in each case optionally fluorine- and/or chlorine-substituted methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or represents methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, dimethylaminosulphonyl or diethylaminosulphonyl.
R4 particularly preferably represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents in each case optionally fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy, represents in each case optionally fluorine- and/or chlorine-substituted methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or represents methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, dimethylaminosulphonyl or diethylaminosulphonyl.
R5 particularly preferably represents hydrogen, hydroxyl, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, fluoro-n-propyl, fluoro-i-propyl, chloro-n-propyl, chloro-i-propyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, trichloroethoxy, chlorofluoroethoxy, chlorodifluoroethoxy, fluorodichloroethoxy, methylthio, ethylthio, n- or i-propylthio, fluoroethylthio, chloroethylthio, difluoroethylthio, dichloroethylthio, chlorofluoroethylthio, chlorodifluoroethylthio, fluorodichloroethylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, dimethylamino, propenylthio, butenylthio, propinylthio, butinylthio, cyclopropyl, cyclopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy.
R6 particularly preferably represents amino, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylamino, dimethylamino, cyclopropyl or cyclopropylmethyl, or together with R5 represents propane-1,3-diyl (trimethylene), butane-1,4-diyl (tetramethylene) or pentane-1,5-diyl (pentamethylene).
Z particularly preferably represents the groupings below 
where Q, R5 and R6 are each as defined above.
A very particularly preferably represents a single bond or represents methylene.
R1 very particularly preferably represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or o-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
R2 very particularly preferably represents hydrogen, cyano, carbamoyl, fluorine, chlorine, bromine, represents in each case optionally cyano-, carbamoyl-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents in each case optionally fluorine- and/or chlorine-substituted methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl.
R3 very particularly preferably represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents in each case optionally fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy, represents in each case optionally fluorine- and/or chlorine-substituted methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or represents methylamino, ethylamino, n- or i-propylamnino, dimethylamino, diethylamino, dimethylaminosulphonyl or diethylaminosulphonyl.
R4 very particularly preferably represents methylsulphonyl, chlorine, methoxy, nitro, trifluoromethyl or methyl.
R5 very particularly preferably represents hydrogen, bromine, chlorine, methyl, ethyl, trifluoromethyl, cyclopropyl, difluoroethyl, methylthio, ethylthio, methoxy, ethoxy, n- or i-propoxy, trifluoroethoxy, methylamino or dimethylamino.
R6 very particularly preferably represents hydrogen, amino, methyl, ethyl, cyclopropyl, dimethylamino methoxy or ethoxy.
R1 most preferably represents cyclopropyl.
R2 most preferably represents hydrogen or cyano.
R3 most preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy.
R5 most preferably represents bromine, methyl, ethyl, methoxy, methylthio, ethoxy, methylsulfonyl or dimethylamino.
R6 most preferably represents amino, methyl, ethyl, cyclopropyl, dimethylamino, methoxy or ethoxy.
Preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings given above as being preferred.
Particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings given above as being particularly preferred.
Very particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings given above as being very particularly preferred.
Most preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings given above as being most preferred.
Part of the subject-matter of the present invention are in particular the compounds of the formulae (IA), (IB) and (IC): 
in which
Z represents the groupings below 
and n, A, Q, R1, R2, R3, R4, R5 and R6 are each as defined above.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
Examples of the compounds of the general formula (I) according to the invention are listed in the groups below.

R3, (R4)n, R5 and R6 have example, the meaning given in the table below:

R3, (R4)n, R5 and R6 have, for example, the meanings given in the table below:

R3, (R4)n, R5 and R6 have, for example, the meanings given above in Group 1.

R3, (R4)n, R5 and R6 have, for example, the meanings given above in Group 2.
The novel substituted benzoyl ketones of the general formula (I) have strong and selective herbicidal activity.
The novel substituted benzoyl ketones of the general formula (I) are obtained when:
(a) ketones of the general formula (II) 
xe2x80x83in which
R1 and R2 are each as defined above,
are reacted with substituted benzoic acids of the general formula (III) 
xe2x80x83in which
n, A, R3, R4 and Z are each as defined above,
if appropriate in the presence of one or more reaction auxiliaries and if appropriate in the presence of one or more diluents,
or when
(b) benzoylisoxazoles of the general formula (IV) 
xe2x80x83in which
n, A, R1, R2, R3, R4 and Z are each as defined above,
are isomerized in the presence of one or more reaction auxiliaries and if appropriate in the presence of one or more diluents,
and electrophilic or nucleophilic substitutions and/or oxidations or reductions within the scope of the definition of the substituents are, if appropriate, subsequently, i.e. after the processes (a) or (b) according to the invention have been carried out, carried out in a customary manner on the resulting compounds of the formula (I), or the compounds of the formula (I) are converted in a customary manner into salts.
The compounds of the formula (I) can be converted by customary methods into other compounds of the formula (I) according to the definition above, for example by nucleophilic substitution (for example R5: Clxe2x86x92OC2H5, SCH3) or by oxidation (for example R5: CH2SCH3xe2x86x92CH2S(O)CH3).
In principle, the compounds of the general formula (I) can also be synthesized as outlined below:
Reaction of ketones of the general formula (II)xe2x80x94abovexe2x80x94with reactive derivatives of the substituted benzoic acids of the general formula (I)xe2x80x94abovexe2x80x94, in particular with appropriate carbonyl chlorides, carboxylic anhydrides, carboxylic acid cyanides, methyl carboxylates or ethyl carboxylatesxe2x80x94if appropriate in the presence of reaction auxiliaries, such as, for example, triethylamine (and, if appropriate, additionally zinc chloride), and if appropriate in the presence of a diluent, such as, for example, methylene chloride: 
Using, for example, ethyl methylsulfonylmethyl ketone and 2-(3-carboxy-5-fluorobenzyl)-5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following formula scheme: 
Using, for example, (5-cyclopropyl-isoxazol-4-yl)-[2-(4-methyl-3-methylthio-5-oxo-4,5-dihydro-[1,2,4]-triazol-1-yl-methyl)-4-trifluoromethyl-phenyl]-methanone as starting material, the course of the reaction in the process (b) according to the invention can be illustrated by the following formula scheme: 
The formula (II) provides a general definition of the ketones to be used as starting materials in the process (a) according to the invention for preparing compounds of the general formula (I). In the general formula (II), R1 and R2 each preferably have those meanings which have already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred, very particularly preferred or most preferred for R1 and R2.
The starting materials of the general formula (II) are known and/or can be prepared by processes known per se (cf. the Preparation Examples).
The formula (III) provides a general definition of the substituted benzoic acids further to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (III), n, A, R3, R4 and Z each preferably have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred, particularly preferred, very particularly preferred or most preferred for n, A, R3, R4 and Z.
The starting materials of the general formula (m), except for 2-(5-carboxy-2,4-dichloro-phenyl)-4-difluoromethyl-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-onexe2x80x94alias 2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-benzoic acid (CAS-Reg.-No. 90208-77-8)xe2x80x94and 2-(5-carboxy-2,4-dichlorophenyl)4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one xe2x80x94alias 2,4-dichloro-5-(4,5-dihydro-3,4-dimethyl-5-oxo-1H-1,2,4-triazol-1-yl)-benzoic acid (CAS-Reg.-No. 90208-76-7)xe2x80x94have hitherto not been disclosed in the literature. Except for 2-(5-carboxy-2,4-dichloro-phenyl)-4-difluoromethyl-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one and 2-(5-carboxy-2,4-dichloro-phenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one (cf. JP-A-58225070xe2x80x94cited in Chem. Abstracts 100:209881, JP-A-02015069xe2x80x94cited in Chem. Abstracts 113:23929) they are, however, part of the subject-matter of an earlier but not prior-published application (cf. DE-A-19833360).
The substituted benzoic acids of the general formula (E) are obtained when benzoic acid derivatives of the general formula (V) 
in which
n, A, R3 and R4 and Z are each as defined above and
X1 represents cyano, carbamoyl or alkoxycarbonyl,
are reacted with water, if appropriate in the presence of a hydrolysis auxiliary, such as, for example, sulfuric acid, at temperatures between 50xc2x0 C. and 120xc2x0 C. (cf. the Preparation Examples).
The benzoic acid derivatives of the general formula (V) required as precursors are known and/or can be prepared by processes known per se (cf. DE-A-3839480, DE-A-4239296, EP-A-597360, EP-A-609734, DE-A-4303676, EP-A-617026, DE-A-4405614, U.S. Pat. No. 5,378,681).
The novel substituted benzoic acids of the general formula (III) are also obtained when halogeno(alkyl)benzoic acids of the general formula (VI) 
in which
n, A, R3 and R4 are each as defined above and
X represents halogen (in particular chlorine or bromine)
are reacted with compounds of the general formula (VII), 
in which
Z is as defined above,
if appropriate in the presence of a reaction auxiliary, such as, for example, triethylamine or potassium carbonate, and if appropriate in the presence of a diluent, such as, for example, acetone, acetonitrile, N,N-dimethyl-formamide or N,N-dimethyl-acetamide, at temperatures between 50xc2x0 C. and 200xc2x0 C. (cf. the Preparation Examples).
In place of the halogeno(alkyl)benzoic acids of the general formula (VI) it is also possible to react the corresponding nitrites, amides and estersxe2x80x94in particular the methyl esters or the ethyl estersxe2x80x94analogously to the method described above with compounds of the general formula (VII). By subsequent hydrolysis according to customary methods, for example by reaction with aqueous/ethanol potassium hydroxide solution, it is then possible to obtain the corresponding substituted benzoic acids.
The halogeno(alkyl)benzoic acids of the formula (VI)xe2x80x94or the corresponding nitriles or estersxe2x80x94required as precursors are known and/or can be prepared by processes known per se (cf. EP-A-90369, EP-A-93488, EP-A-399732, EP-A-480641, EP-A-609798, EP-A-763524, DE-A-2126720, WO-A-93/03722, WO-A-97/38977, U.S. Pat. No. 3,978,127, U.S. Pat. No. 4,837,333).
The compounds of the general formula (VII) further required as precursors are known and/or can be prepared by processes known per se.
The process (a) according to the invention for preparing the novel substituted benzoyl ketones of the general formula (I) is, if appropriate, carried out using one or more reaction auxiliaries.
Examples of these which may be mentioned are sodium cyanide, potassium cyanide, acetone cyanohydrin, imidazole, triazole, diethyl cyanophosphonate, 2-cyano-2-(trimethylsilyloxy)-propane and trimethylsilyl cyanide.
Particularly suitable reaction auxiliaries which may be mentioned are diethyl cyanophosphonate and trimethylsilyl cyanide.
The processes (a) and (b) according to the invention for preparing the novel substituted benzoyl ketones of the general formula (I) are, if appropriate, carried out using a (further) reaction auxiliary. Suitable (further) reaction auxiliaries for the processes according to the invention are, in general, basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2.2.2]-octane (DABCO), 1,5-diazabicyclo[4.3.0]-non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).
Suitable diluents for carrying out the processes (a) and (b) according to the invention are especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride or 1,2-dichloroethane; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide.
When carrying out the processes (a) and (b) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reactions are carried out at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 10xc2x0 C. and 120xc2x0 C.
The processes (a) and (b) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
For carrying out the processes (a) and (b) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to employ a relatively large excess of one of the components. The reaction is generally carried out in a suitable diluent in the presence of a dehydrating agent, and the reaction mixture is generally stirred at the required temperature for several hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Aegilops, Phalaris.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the active compounds according to the invention are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree growth. Equally, the active compounds according to the invention can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.
The compounds of the formula (I) according to the invention have strong herbicidal activity and a broad activity spectrum when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use dyestuffs, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazon, benzobicyclon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon(-ethyl), cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-P-butyl), fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-p-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, picolinafen, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin, triflusulfuron, tritosulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.
The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.